CN102585489A - Polyamide resin composition and molded product using the same - Google Patents
Polyamide resin composition and molded product using the same Download PDFInfo
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- CN102585489A CN102585489A CN2011104316071A CN201110431607A CN102585489A CN 102585489 A CN102585489 A CN 102585489A CN 2011104316071 A CN2011104316071 A CN 2011104316071A CN 201110431607 A CN201110431607 A CN 201110431607A CN 102585489 A CN102585489 A CN 102585489A
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- polyamide
- polyamide resin
- resin composition
- crystalline
- amilan
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed are a polyamide resin composition that includes (A) a crystalline polyamide mixed resin including an aliphatic group and at least two different crystalline polyamide resins, (B) a non-crystalline polyamide resin including an aromatic group, and (C) a glass fiber, and a molded product manufacture using the same.
Description
Related application
Right of priority and rights and interests that the korean patent application that the application requires to submit to Korea S Department of Intellectual Property on December 21st, 2010 is 10-2010-0131828 number, its full content is herein incorporated by reference.
Technical field
The present invention relates to a kind of Amilan polyamide resin composition and the moulded product that uses said compsn.
Background technology
Polyamide resin prepares to realize its mechanical characteristics and thermal property through comprising inorganic materials such as spun glass; And be mainly used in UTH (the under the hood) parts of producing automobile; Yet; Inorganic materials can cause the stress difference on the product because of anisotropy, thereby causes the quality problems of product.
Summary of the invention
An illustrative embodiments provides a kind of excellent properties equilibrated Amilan polyamide resin composition that has between mechanical property, thermotolerance and the dimensional stability.
Another embodiment provides a kind of moulded product that uses said Amilan polyamide resin composition to make.
According to an embodiment; A kind of Amilan polyamide resin composition is provided; Comprise: (A) about 20wt% comprises first crystalline polyamide resin (A-1) with aliphatic group and the second crystalline polyamide resin (A-2) with aliphatic group to the crystalline polyamide hybrid resin of about 80wt%; (B) about 1wt% is to the noncrystalline polyamide resin with aromatic group of about 30wt%; (C) about 10wt% is to the spun glass of about 50wt%, wherein (A-1) first crystalline polyamide resin and (A-2) the second crystalline polyamide resin differ from one another.
The first crystalline polyamide resin (A-1) and the second crystalline polyamide resin (A-2) can differ from one another, and comprise polyamide 6 independently, polymeric amide 11, polymeric amide 12, polymeric amide 46, polyamide 66, polyamide 69, polyamide 6 10, polyamide 6 12, polyamide 6/610, polyamide 6/66, polyamide 6/12, polyphthalamide, polyaramide or their combination.
The first crystalline polyamide resin (A-1) and the second crystalline polyamide resin (A-2) mixed to about 3: 1 weight ratio with about 1: 3.
Said noncrystalline polyamide resin (B) can comprise polyamide 6 T, polymeric amide 9T, polyamide 6 I, polymeric amide MXD6, polymeric amide M5T, polyamide 6/6T, polyamide 66/6T, polyamide 66/6I, polyamide 6 T/6I, polyamide 6 T/12, polyamide 66/6T/6I, polyamide 6 T/M5T or their combination.
Said crystalline polyamide hybrid resin (A) and said noncrystalline polyamide resin (B) can about 5: 1 mix to about 15: 1 weight ratio.
Said spun glass (C) can comprise that (C-1) has the spun glass of circular cross section and the spun glass that (C-2) has oval cross section.
Said spun glass (C-1) with circular cross section and said has the spun glass (C-2) of oval cross section can about 1: 4 to be mixed to about 4: 1 weight ratio.
Said Amilan polyamide resin composition can have the lateral shrinkage less than about 0.90%.
According to another embodiment, a kind of moulded product of being made by said Amilan polyamide resin composition is provided.
Below, will specify other embodiment.
Above-mentioned Amilan polyamide resin composition has the excellent properties balance between mechanical property, thermotolerance and the dimensional stability; Thereby can be applicable to multiple moulded product; Especially plastics externally applied product, the for example UTH of electronic unit, automobile (under the hood) parts etc.
Embodiment
Below with the detailed description exemplary embodiment.Yet these embodiments only are exemplary, and the invention is not restricted to this.
According to an embodiment, a kind of Amilan polyamide resin composition is provided, comprising: (A) comprise the noncrystalline polyamide resin of crystalline polyamide hybrid resin (B) of at least two kinds of different crystalline polyamide resins and (C) spun glass.
Below will specify the exemplary compositions that comprises in the Amilan polyamide resin composition according to an embodiment.
(A) crystalline polyamide hybrid resin
The crystalline polyamide hybrid resin can be through mixing at least two kinds of different crystalline polyamide resins.
The crystalline polyamide hybrid resin can comprise the first crystalline polyamide resin and the second crystalline polyamide resin different with the first crystalline polyamide resin.The first crystalline polyamide resin and the second aliphatic crystalline polyamide resin all are the polyamide compounds that main chain contains aliphatic group.
The first crystalline polyamide resin and the second aliphatic crystalline polyamide resin can differ from one another; And can comprise for example polyamide 6, polymeric amide 11, polymeric amide 12, polymeric amide 46, polyamide 66, polyamide 69, polyamide 6 10, polyamide 6 12, polyamide 6/610, polyamide 6/66, polyamide 6/12, polyphthalamide, polyaramide or their combination, but be not limited thereto.In one embodiment, can the mixture of polyamide 6 and polyamide 66 polymeric amide be used as the crystalline polyamide hybrid resin.The mixture of polyamide 6 and polyamide 66 can improve plasticity and outward appearance, and reduces production costs.
The first crystalline polyamide resin mixes to about 3: 1 weight ratio with about 1: 3 with the second crystalline polyamide resin, particularly mixes with about 1: 2 to 2: 1 weight ratio.When the first crystalline polyamide resin mixed in above-mentioned scope with the second aliphatic crystalline polyamide resin, Amilan polyamide resin composition can have the excellent properties balance between mechanical property, thermotolerance and the dimensional stability.
The first crystalline polyamide resin and the second crystalline polyamide resin have about 30% or higher percent crystallinity, for example about 30% to about 40% respectively.
Based on the gross weight of Amilan polyamide resin composition, the content of crystalline polyamide hybrid resin can be about 20wt% to about 80wt%, is specially about 30wt% to about 60wt%.In the time of in the crystalline polyamide hybrid resin is included in above-mentioned scope, Amilan polyamide resin composition can have the excellent properties balance between mechanical property, thermotolerance, dimensional stability and the plasticity.
(B) noncrystalline polyamide resin
Noncrystalline polyamide resin is that fusing point is the polyamide compound that contains aryl on about 180 ℃ or higher and its main chain.
Particularly, noncrystalline polyamide resin can be through comprising that extremely the dicarboxylicacid and the aliphatic series/alicyclic diamine polycondensation of about 100mol% aromatic dicarboxylic acid prepare about 10mol%.
Aromatic dicarboxylic acid can be specially the m-phthalic acid that terephthalic acid that following Chemical formula 1 a representes or following Chemical formula 1 b represent.
[Chemical formula 1 a]
[Chemical formula 1 b]
Aliphatic series/alicyclic diamine can be C4 to C20 diamine compound.
The instance of noncrystalline polyamide resin can comprise through polycondensation hexanediamine and terephthalic acid and prepares polyamide 6 T.Polyamide 6 T can comprise the repeating unit that following Chemical formula 2 is represented.
[Chemical formula 2]
Noncrystalline polyamide resin can be included in its main chain and have the polyamide compound of aryl and the multipolymer that has the polyamide compound of aliphatic group at its main chain.
For example, noncrystalline polyamide resin can comprise for example polyamide 6 T, polymeric amide 9T, polyamide 6 I, polymeric amide MXD6, polymeric amide M5T, polyamide 6/6T, polyamide 66/6T, polyamide 66/6I, polyamide 6 T/12, polyamide 66/6T/6I, polyamide 6 T/M5T or their combination.
Above-mentioned noncrystalline polyamide resin has about 5% or lower percent crystallinity, for example about 0% to about 5%.
Gross weight based on Amilan polyamide resin composition; The content of noncrystalline polyamide resin can be about 1wt% to about 30wt%; Be specially about 8wt% to about 15wt%, when the content of noncrystalline polyamide resin was in above-mentioned scope, the dimensional stability of Amilan polyamide resin composition can improve.
Crystalline polyamide hybrid resin (A) and noncrystalline polyamide resin (B) can mix to about 15: 1 weight ratio with about 5: 1, specifically mix to about 13: 1 weight ratio with about 6: 1.When crystalline polyamide hybrid resin and noncrystalline polyamide resin mixed in aforementioned proportion, Amilan polyamide resin composition can have the excellent properties balance between mechanical property, thermotolerance and the dimensional stability.
(C) spun glass
Spun glass can have the diameter and about 1.5mm length to about 13mm of about 5 μ m to about 30 μ m.The diameter of spun glass and length are in above-mentioned scope the time, and spun glass is easy to put into forcing machine, and brings fabulous mechanical property.
Spun glass can have circular cross section and oval cross section.
Long-width ratio with spun glass of circular cross section can be about 1.Aspect ratio is defined as longest diameter and the shortest diameter ratio in the xsect.
The long-width ratio of spun glass with oval cross section is greater than about 1.Particularly, the long-width ratio with spun glass of oval cross section is about 1.5 or higher, more specifically is about 2 to about 8, further more specifically is about 2 to about 6.
Spun glass with circular cross section mixes with about 1: 4 to 4: 1 weight ratio with the spun glass with oval cross section, particularly mixes with about 1: 2 to 2: 1 weight ratio.When spun glass mixed in aforementioned proportion, the dimensional stability of Amilan polyamide resin composition can improve.
The surface of spun glass can scribble predetermined material, preventing the reaction between crystalline polyamide hybrid resin and the noncrystalline polyamide resin, and improves humidity.
Above-mentioned coated material can change overall flow property, mechanical property of Amilan polyamide resin composition etc.The kind of the coated material that is coated with on the fiberglass surfacing is known in those skilled in the art.
Based on the gross weight of Amilan polyamide resin composition, the content of spun glass can be about 10wt% to about 50wt%, is specially about 20wt% to about 40wt%.When the content of spun glass was in above-mentioned scope, Amilan polyamide resin composition can have the excellent properties balance between mechanical property, thermotolerance and the dimensional stability.
(D) other additive
Amilan polyamide resin composition further can comprise the additive of antiseptic-germicide, thermo-stabilizer, inhibitor, parting agent, photostabilizer, tensio-active agent, coupling agent, softening agent, admixture (admixture), tinting material, stablizer, lubricant, static inhibitor, colouring aid, fireproofing agent, weather resisting agent, ultraviolet (UV) absorption agent, ultraviolet (UV) blocking agent, nucleator, bonding agent, tackiness agent, or their combination.
Inhibitor can comprise phenol, phosphorous acid ester, thioether or amine inhibitor.Parting agent can comprise metal-salt, montanic acid ester type waxes or the polyethylene wax of fluoropolymer, silicone oil, stearic metal-salt, montanic acid.Weather resisting agent can comprise diphenyl ketone type or amine type weather resisting agent, and tinting material can comprise dyestuff or pigment.Ultraviolet (UV) line blocking agent can comprise titanium oxide (TiO
2) or carbon black.Nucleator can comprise mica and clay.
Only otherwise make the Amilan polyamide resin composition degradation, can comprise the additive of predetermined amount.In one embodiment, based on the Amilan polyamide resin composition of 100 weight parts, content of additive can be about 40 weight parts or lower, and for example about 0.1 to about 30 weight parts.
Amilan polyamide resin composition can prepare through the known method for preparing thermoplastic resin composition, for example mixes each component and additive according to an embodiment simultaneously.Mixture is melted extrudes and processes particle.
The TD of Amilan polyamide resin composition (laterally) shrinking percentage can be specially about 0.80% to about 0.88% less than about 0.90%.The TD shrinking percentage is through using the sample by the Amilan polyamide resin composition preparation; Keep being injected into 10 ounces injection moulding machine in the film cast gate mould of 6 ＂ * 6 ＂ and 1/8 ＂ thickness at 80 ℃, then its indoor placement of fixed temperature and humidity in no external pressure, 23 ℃ and 50% humidity was measured in 24 hours.
According to another embodiment, the moulded product that uses aforementioned Amilan polyamide resin composition to make is provided.In other words, use Amilan polyamide resin composition to make moulded product through several different methods such as for example injection moulding, blow molding, extrusion molding, thermoformings.Particularly, Amilan polyamide resin composition can need advantageously be applied to the moulded product of mechanical property, thermotolerance and dimensional stability, especially plastics externally applied product, the for example UTH of electronic unit, automobile (under the hood) parts etc.
Following examples will illustrate in greater detail the present invention.Yet, it should be understood that the present invention is not subject to these embodiment.
Amilan polyamide resin composition according to an embodiment comprises following each component.
(A) crystalline polyamide (PA) hybrid resin
(A-1) first crystalline polyamide (PA) resin
For polyamide 6, use the TP-4210 that makes by Zigsheng Industrial ltd.
(A-2) second crystalline polyamide (PA) resin
For polyamide 66, use the Leona 1200 that makes by Asahi-Kasei ltd.
(B) noncrystalline polyamide (PA) resin
(C) spun glass
(C-1) use the CS321-EC10-3 that makes by KCC spun glass as the about 3mm of length, the about 13 μ m of diameter and long-width ratio about 1.
(C-2) use the CSG 3PA-820 that makes by Nitto Boseki ltd spun glass as about 4 (the about 28 μ m of longest diameter, about 7 μ m of the shortest diameter) of long-width ratio and the about 3mm of length.
Embodiment 1～5 and Comparative Examples 1～9
Each Amilan polyamide resin composition of embodiment 1～5 and Comparative Examples 1～9 prepares with the aforementioned component in the following table 1 listed composition.
Mix each component to have the composition in the following table 1, extrude with common biaxial extruder, be configured as particle then at 220 ℃.
Experimental example
The specimen preparation of ASTM dumb-bell shape is following: with particle 80 ℃ dry 2 hours down, with 6 ounces injection moulding machine injection moulding, and the setting barrel temperature is 210 ℃, molding temperature is 60 ℃.The performance of working sample.The result is shown in Table 1.
(1) tensile strength: measure according to ASTM D638.
(2) flexural strength: measure according to ASTM D790.
(3) modulus in flexure: measure according to ASTM D790.
(4) heat-drawn wire (HDT): measure according to ASTM D648.
(5) TD (laterally) shrinking percentage: when 80 ℃ keep the film cast gate mould of 6 ＂ * 6 ＂, 1/8 ＂ thickness, Amilan polyamide resin composition is injected 10 ounces injection moulding machine, then with gains the indoor placement of fixed temperature and humidity of no external pressure, 23 ℃ and 50% humidity 24 hours.Mensuration makes the shrinking percentage of sample and is expressed as per-cent (%) unit.
(table 1)
With reference to table 1; With the Comparative Examples that comprises the crystalline polyamide resin 6,7 and 9, do not comprise the Comparative Examples 1 to 7 of noncrystalline polyamide resin and do not comprise that the Comparative Examples 8 of spun glass compares, comprise that the embodiment 1 to 5 of the crystalline polyamide hybrid resin with at least two kinds of different crystalline polyamide resins, noncrystalline polyamide resin and spun glass has the excellent properties balance between mechanical property, thermotolerance and the dimensional stability.
Particularly, comprise that the first and second crystalline polyamide resins are that the embodiment 1 to 5 of the mixture of proper ratio has mechanical property, the excellent properties balance between thermotolerance and the dimensional stability.In addition; When the crystalline polyamide hybrid resin that contains at least two kinds of different crystalline polyamide resins mixes with noncrystalline polyamide resin when preparing Amilan polyamide resin composition with proper ratio, Amilan polyamide resin composition has confirmed to have the excellent properties balance between mechanical property, thermotolerance and the dimensional stability.In addition, when two kinds of different spun glass were mixed with Amilan polyamide resin composition with proper ratio, Amilan polyamide resin composition had confirmed to have splendid dimensional stability.
Although combined to think at present that enforceable illustrative embodiments explained the present invention, it should be understood that to the invention is not restricted to disclosed embodiment, on the contrary, be intended to cover the various modifications and the equivalent arrangements that comprise within the spirit and scope of the present invention.Therefore, aforementioned embodiments is interpreted as exemplary, and does not limit the present invention in any way.
Claims (9)
1. Amilan polyamide resin composition comprises:
(A) the crystalline polyamide hybrid resin of 20wt% to 80wt% comprises first crystalline polyamide resin (A-1) with aliphatic group and the second crystalline polyamide resin (A-2) with aliphatic group;
(B) the noncrystalline polyamide resin of 1wt% to 30wt% with aromatic group; With
(C) spun glass of 10wt% to 50wt%,
Wherein said first crystalline polyamide resin (A-1) and the said second crystalline polyamide resin (A-2) differ from one another.
2. Amilan polyamide resin composition according to claim 1; Wherein said first crystalline polyamide resin (A-1) and the said second crystalline polyamide resin (A-2) differ from one another, and comprise polyamide 6 independently, polymeric amide 11, polymeric amide 12, polymeric amide 46, polyamide 66, polyamide 69, polyamide 6 10, polyamide 6 12, polyamide 6/610, polyamide 6/66, polyamide 6/12, polyphthalamide, polyaramide or their combination.
3. Amilan polyamide resin composition according to claim 1, wherein said first crystalline polyamide resin (A-1) and the said second crystalline polyamide resin (A-2) mix with 1: 3 to 3: 1 weight ratio.
4. Amilan polyamide resin composition according to claim 1, wherein said noncrystalline polyamide resin (B) comprises polyamide 6 T, polymeric amide 9T, polyamide 6 I, polymeric amide MXD6, polymeric amide M5T, polyamide 6/6T, polyamide 66/6T, polyamide 66/6I, polyamide 6 T/6I, polyamide 6 T/12, polyamide 66/6T/6I, polyamide 6 T/M5T or their combination.
5. Amilan polyamide resin composition according to claim 1, wherein said crystalline polyamide hybrid resin (A) and said noncrystalline polyamide resin (B) mix with 5: 1 to 15: 1 weight ratio.
6. Amilan polyamide resin composition according to claim 1, wherein said spun glass (C) comprise that (C-1) has the spun glass of circular cross section and the spun glass that (C-2) has oval cross section.
7. Amilan polyamide resin composition according to claim 6, wherein said spun glass with circular cross section mixes with 1: 4 to 4: 1 weight ratio with the spun glass with oval cross section.
8. Amilan polyamide resin composition according to claim 1, wherein said Amilan polyamide resin composition has the lateral shrinkage less than 0.90%.
9. moulded product, said moulded product uses any described Amilan polyamide resin composition manufacturing in the claim 1 to 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100131828A KR101466278B1 (en) | 2010-12-21 | 2010-12-21 | Polyamide resin composition and molded product using the same |
| KR10-2010-0131828 | 2010-12-21 |
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| CN102585489A true CN102585489A (en) | 2012-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011104316071A Pending CN102585489A (en) | 2010-12-21 | 2011-12-21 | Polyamide resin composition and molded product using the same |
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| US (1) | US8618209B2 (en) |
| KR (1) | KR101466278B1 (en) |
| CN (1) | CN102585489A (en) |
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| CN106751793A (en) * | 2016-11-18 | 2017-05-31 | 江苏沃特新材料科技有限公司 | High surface gloss high-dimensional stability polyamide compoiste material and preparation method thereof |
| CN109825074A (en) * | 2019-01-23 | 2019-05-31 | 江翼明 | A kind of high rigidity semiaromatic polyamide composition and preparation method thereof |
| CN109825073A (en) * | 2019-01-24 | 2019-05-31 | 广东壹豪新材料科技股份有限公司 | A kind of preparation method of high temperature resistance and high strength material |
| CN110615984A (en) * | 2019-09-26 | 2019-12-27 | 安特普工程塑料（苏州）有限公司 | Low-mold-temperature injection-molded glass fiber reinforced high-temperature nylon and production process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101466278B1 (en) | 2014-11-27 |
| US8618209B2 (en) | 2013-12-31 |
| KR20120089912A (en) | 2012-08-16 |
| US20120157606A1 (en) | 2012-06-21 |
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